EP2896596A1 - Reformierungsvorrichtung und reformierungsverfahren, vorrichtung zur herstellung chemischer produkte mit einer reformierungsvorrichtung und verfahren zur herstellung chemischer produkte - Google Patents

Reformierungsvorrichtung und reformierungsverfahren, vorrichtung zur herstellung chemischer produkte mit einer reformierungsvorrichtung und verfahren zur herstellung chemischer produkte Download PDF

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Publication number
EP2896596A1
EP2896596A1 EP13837204.0A EP13837204A EP2896596A1 EP 2896596 A1 EP2896596 A1 EP 2896596A1 EP 13837204 A EP13837204 A EP 13837204A EP 2896596 A1 EP2896596 A1 EP 2896596A1
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Prior art keywords
heat
reforming
gas
unit
raw material
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English (en)
French (fr)
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EP2896596A4 (de
Inventor
Mikiya Sakurai
Naoya OKUZUMI
Ryota Shimura
Shuichi Miyamoto
Yoshio Seiki
Hiroyuki Osora
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Mitsubishi Heavy Industries Ltd
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Mitsubishi Heavy Industries Ltd
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    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
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    • C01C1/026—Preparation of ammonia from inorganic compounds
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    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
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    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
    • C07C273/10—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds combined with the synthesis of ammonia
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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    • C07C31/04—Methanol
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
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    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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    • C01B2203/1258—Pre-treatment of the feed
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/50—Improvements relating to the production of bulk chemicals
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Definitions

  • the present invention relates to a reforming device that reforms a natural gas by using the natural gas as a fuel of a reformer for reforming the natural gas or the like, and a device for manufacturing chemical products equipped with the same.
  • a reformed gas obtained by reforming the natural gas or the like in the reformer is used (for example, see Patent Literatures 1 and 2).
  • the natural gas or the like is reformed in the reformer to convert the natural gas to the reformed gas, before supplying the natural gas to the reformer, a part of the natural gas is extracted and used as fuel of the reformer, and the natural gas supplied to the reformer is reformed.
  • Patent Literatures 1 and 2 in the method for manufacturing methanol and ammonia which have been conventionally used, in general, the natural gas is first compressed to a reforming pressure. Moreover, a part of the natural gas which has not been desulfurized is extracted before compressing the natural gas and is used as fuel of the reformer. Thereafter, for improving production efficiency of methanol and ammonia, in order to improve a quantity of heat recovery from the reformer flue gas and improve the thermal efficiency when reforming the natural gas, there is a need to further improve the reforming device.
  • the present invention has been made in view of the above-described problems, and an object thereof is to provide a reforming device and a reforming method capable of improving the thermal efficiency when reforming the natural gas, a manufacturing device of chemical products equipped with the reforming device, and a method for chemical products.
  • a reforming device including: a first compression unit that compresses a raw material gas containing hydrocarbon and sulfur; a first heat-exchange unit that heats the compressed raw material gas; a desulfurization unit that removes sulfur content contained in the heated raw material gas; a reforming unit that reforms the hydrocarbon in the raw material gas to either one or both of H 2 and CO or H 2 and CO 2 to generate a reformed gas containing either one or both of H 2 and CO or H 2 and CO 2 ; a raw material gas branching line that extracts a part of the compressed raw material gas from either one or both of an upstream side and a downstream side of the desulfurization unit with respect to a flow direction of the raw material gas, and supplies the part of the compressed raw material gas as a combustion fuel used for heating in the reforming unit; a flue gas discharging line that discharges a flue gas, which is generated by combustion in the reform
  • the reforming device has a first reforming unit that supplies vapor to the raw material gas to primarily reform the hydrocarbon in the raw material gas to either one or both of H 2 and CO or H 2 and CO 2 , and a second reforming unit that secondarily reforms the hydrocarbon in the raw material gas after the primary reforming in the first reforming unit to either one or both of H 2 and CO or H 2 and CO 2 to be a reformed gas, using the combustion air and the compressed raw material gas supplied from the raw material gas branching line.
  • a third heat exchanger configured to heat-exchange feed water supplied to a steam generation unit with the flue gas is provided between the first heat exchange unit and the second heat exchange unit.
  • the reforming device according to the third aspect, further including: a fourth heat exchanger that is provided in the raw material gas branching line to heat-exchange the compressed raw material gas before being introduced into the first heat exchanger with a part of the branched raw material gas.
  • the reforming device including any one or both of: a denitrification unit that is provided between the reforming unit of the flue gas discharging line and the heat exchange unit to remove NOx contained in the flue gas that is generated in the reforming unit; and a CO 2 recovery unit that is provided on the downstream side of the heat exchange unit with respect to the flow direction of the flue gas of the flue gas discharging line to remove CO 2 contained in the flue gas.
  • a device for manufacturing chemical products including: the reforming device according to any one of the first to fifth aspects; and a chemical product generation unit that manufactures chemical products using the reformed gas.
  • the device for manufacturing chemical products according to the sixth aspect, wherein the chemical product generation unit is an ammonia synthesis unit that synthesizes ammonia using the reformed gas which has been reformed.
  • the device for manufacturing chemical products according to the seventh aspect, wherein the chemical product generation unit is a urea synthesis unit that synthesizes urea using the obtained ammonia.
  • the device for manufacturing chemical products according to the sixth aspect, wherein the chemical product generation unit is a methanol synthesis unit that synthesizes methanol using the reformed gas which has been reformed.
  • a reforming method including: a first heat-exchange step of heating a raw material gas containing compressed hydrocarbon and sulfur; a desulfurization step of removing sulfur content contained in the heated raw material gas; a reforming step of reforming the hydrocarbon in the raw material gas to either one or both of H 2 and CO or H 2 and CO 2 to generate a reformed gas containing either one or both of H 2 and CO or H 2 and CO 2 ; and a second heat-exchange step of heat-exchanging a combustion air used for heating in the reforming step with the flue gas that is heat-exchanged in the first heat-exchange step, wherein the compressed raw material gas is extracted from either one or both of an upstream side and a downstream side of the desulfurization step with respect to a flow direction of the raw material gas, and is supplied as a combustion fuel used for heating in the reforming step, and the flue gas generated by combustion in the reforming step is discharged from the reforming step,
  • the reforming method according to the tenth aspect wherein a third heat-exchange step of heat-exchanging feed water supplied to a steam generation unit with the flue gas is provided between the first heat-exchange step and the second heat-exchange step.
  • the reforming method according to the eleventh aspect further including: a fourth heat-exchange step that is provided in the raw material gas branching line to heat-exchange the compressed raw material gas introduced into the first heat-exchange step with a part of the branched raw material gas.
  • a method for manufacturing chemical products including: the reforming step according to any one of the tenth to eleventh aspects; and a chemical product generation step of manufacturing chemical products using the reformed gas.
  • the method for manufacturing chemical products according to the thirteenth aspect wherein the chemical product generation step is an ammonia synthesizing step of synthesizing ammonia using the reformed gas which has been reformed.
  • the method for manufacturing chemical products according to the fourteenth aspect wherein the chemical product generation step is a urea synthesizing step of synthesizing urea using the obtained ammonia.
  • the method for manufacturing chemical products according to the thirteenth aspect wherein the chemical product generation step is a methanol synthesizing step of synthesizing methanol using the reformed gas which has been reformed.
  • FIG. 1 is a schematic diagram of a reforming device according to the first embodiment of the present invention.
  • a reforming device 10 has a compressor (compression unit) 11, a first heat exchanger (heat exchange unit) 12, a desulfurization device (desulfurization unit) 13, a reformer (reforming unit) 14, a denitrification device (denitrification unit) 15, a second heat exchanger 16, a cooling device 17, a CO 2 recovery device (CO 2 recovery unit) 18, a raw material gas branching line L11, and a flue gas discharging line L12.
  • a natural gas 21 is used as a raw material gas containing hydrocarbon and sulfur
  • the raw material gas is not limited thereto, any raw material gas containing hydrocarbon may be used, and for example, a liquefied petroleum gas (LPG), a synthetic gas such as butane or naphtha obtained from other hydrocarbon, a natural gas liquid (NGL) produced due to production of crude oil and natural gas, methane hydrate or the like is adopted.
  • LPG liquefied petroleum gas
  • NNL natural gas liquid
  • the compressor 11 is intended to compress the natural gas 21, and raises the natural gas 21 to a predetermined pressure.
  • the natural gas 21 is supplied to the compressor 11 through a raw material gas supply line L13-1. After the natural gas 21 is raised to a predetermined pressure in the compressor 11 to become a high temperature, the natural gas 21 is supplied to the first heat exchanger 12 through the raw material gas supply line L13-2.
  • the first heat exchanger 12 is intended to heat the compressed natural gas 21.
  • the first heat exchanger 12 is provided in a flue gas discharging line L12.
  • the first heat exchanger 12 circulates flue gas 22 inside the duct by setting a duct side as a secondary side, and a tube (heat transfer tube) side of the first heat exchanger 12 is set to a primary side.
  • the first heat exchanger 12 circulates the flue gas 22 discharged from the reformer 14 as a heating medium inside the duct, as described below.
  • the first heat exchanger 12 uses the flue gas 22 to be supplied to the outer circumference of the heat transfer tube as a heat source, and circulates the natural gas 21 inside the heat transfer tube to heat the natural gas 21.
  • the first heat exchanger 12 is not limited to a convection coil type heat exchanger, and any heat exchanger which is capable of performing the indirect heat exchange between the natural gas 21 and the flue gas 22 may be used.
  • the natural gas 21 is heated by being heat-exchanged with the flue gas 22 in the first heat exchanger 12
  • the natural gas 21 is supplied to the desulfurization device 13 through the raw material gas supply line L13-3.
  • the desulfurization device 13 is intended to remove the sulfur content (S content), such as hydrogen sulfide (H 2 S) contained in the heated natural gas 21, and organosulfur compound.
  • S content sulfur content
  • H 2 S hydrogen sulfide
  • a conventionally known device is used as the desulfurization device 13, and either wet type or dry type can be used.
  • the desulfurization device 13 is an absorber that removes the S content in the natural gas 21 in a wet process
  • lime slurry an aqueous solution prepared by dissolving limestone powder in water
  • the lime slurry is supplied to the absorber bottom of the desulfurization device 13.
  • the lime slurry supplied to the absorber bottom of the desulfurization device 13 is sent to a plurality of nozzles in the desulfurization device 13 via an absorbent feed line or the like, and is ejected, for example, toward an absorber top side of the absorber from the nozzle.
  • the S content in the natural gas 21 is absorbed by the lime slurry and is separated and removed from the natural gas 21.
  • the S content in the natural gas 21 generates a reaction with the lime slurry represented by the following formula (1).
  • the lime slurry which has absorbed the S content in the natural gas 21, is oxidized by air (not illustrated) supplied to the absorber bottom of the desulfurization device 13, and generates the reaction with air represented by the following formula (2).
  • the S content in the natural gas 21 is captured in the form of gypsum CaSO 4 ⁇ 2H 2 O in the desulfurization device 13.
  • the natural gas 21 purified by the lime slurry is discharged from the absorber top side of the desulfurization device 13. Thereafter, the natural gas 21 is supplied into the reformer 14 through the raw material gas supply line L13-4.
  • the raw material gas supply line L13-4 is connected to a vapor supply line L14.
  • a vapor 24 is supplied into the raw material gas supply line L13-4 through the vapor supply line L14, and is mixed with the natural gas 21. After the natural gas 21 is mixed with the vapor 24 in the vapor supply line L14, the mixture is supplied into the reformer 14.
  • the reformer 14 is intended to reform hydrocarbon in the natural gas 21 to either one or both of H 2 and CO or H 2 and CO 2 , and generate a reformed gas 23 containing either one or both of H 2 and CO or H 2 and CO 2 .
  • the reformer 14 has a main body 14a, a catalyst reaction tube 14b, and a burner 14c.
  • the catalyst reaction tube 14b is provided inside the main body 14a, and a reforming catalyst layer having a reforming catalyst is provided inside the catalyst reaction tube 14b.
  • the burner 14c is provided inside the main body 14a, and heats the catalyst reaction tube 14b, by combusting a combustion air 26 to generate a flue gas 22.
  • the burner 14c is connected to the air supply line L15.
  • the combustion air 26 is supplied to the burner 14c through the air supply line L15.
  • the combustion air 26 is supplied to the reformer 14.
  • the catalyst reaction tube 14b is heated by the flue gas 22, the natural gas 21 comes into contact with the reforming catalyst when passing through the reforming catalyst layer of the catalyst reaction tube 14b, and thus, as in the following formulas (3) and (4), hydrocarbon in the natural gas 21 is reformed to H 2 and CO or H 2 and CO 2 .
  • a reformed gas 23 containing either one or both of H 2 and CO or H 2 and CO 2 is produced.
  • the gas temperature of the reformed gas 23 is in the range of, for example, 400°C to 1000°C. CH 4 + H 2 O ⁇ CO + 3H 2 (3) CH 4 + 2H 2 O ⁇ CO 2 + 4H 2 (4)
  • the raw material gas branching line L11 connects a downstream side of the desulfurization device 13 with the air supply line L15.
  • the raw material gas branching line L11 extracts a part of the natural gas 21 compressed by the compressor 11 from the downstream side of the desulfurization device 13 with respect to the flow direction of the natural gas 21 as a branch gas 21a, and mixes the branch gas 21a with the flue gas 22 passing through the air supply line L15.
  • the branched branch gas 21a since the S content contained in the natural gas 21 is removed by the desulfurization device 13, the natural gas 21 containing no S content is supplied to the air supply line L15.
  • the reformed gas 23 produced in the reformer 14 is used as a raw material gas for synthesizing hydrogen, liquid hydrocarbon, methanol, ammonia or the like. Also, the flue gas 22 discharged from the reformer 14 is supplied to a denitrification device 15 through the flue gas discharging line L12.
  • the flue gas discharging line L12 is a line for discharging the flue gas 22 which is generated by combusting the fuel containing the natural gas 21 extracted to the raw material gas branching line L11 as a fuel, using the combustion air 26 in the reformer 14.
  • the denitrification device 15, and a reducing agent injector 28 located on the upstream side of the denitrification device 15 are provided.
  • a reducing agent 29 is supplied to the flue gas 22 from the reducing agent injector 28.
  • the reducing agent 29 for example, ammonia (NH 3 ), urea (NH 2 (CO)NH 2 ), ammonium chloride (NH 4 Cl) and the like are used.
  • the reducing agent 29 is supplied to the flue gas discharging line L12 as a solution or gas containing the reducing agent 29.
  • a solution containing the reducing agent 29 is supplied to the flue gas discharging line L12, droplets of the solution containing the reducing agent 29 are vaporized by evaporation by high-temperature ambient temperature of the flue gas 22.
  • the flue gas 22 is supplied to the denitrification device 15 through the flue gas discharging line L12 in a state of containing the reducing agent 29.
  • the denitrification device 15 is provided between the reformer 14 of the flue gas discharging line L12 and the first heat exchanger 12 to remove the nitrogen oxides (NOx) contained in the flue gas 22 generated in the reformer 14.
  • a conventionally known device is used, and for example, as the denitrification device 15, a device equipped with a denitrification catalyst layer in which a denitrification catalyst for removing NOx in the flue gas 22 is filled is used.
  • the flue gas 22 is supplied to the first heat exchanger 12. Moreover, in the first heat exchanger 12, as described above, the flue gas 22 is heat-exchanged with the natural gas 21 to heat the natural gas 21. Thereafter, the flue gas 22 is supplied to the second heat exchanger 16 from the first heat exchanger 12 through the flue gas discharging line L12.
  • the second heat exchanger 16 is intended to heat the combustion air 26. Like the first heat exchanger 12, the second heat exchanger 16 is provided in the flue gas discharging line L12. As the second heat exchanger 16, like the first heat exchanger 12, a convection coil type heat exchanger is used. The second heat exchanger 16 circulates the flue gas 22 inside the duct by setting the duct side as a secondary side, and circulates the combustion air 26 inside the heat transfer tube by setting the tube (heat transfer tube) side as a primary side. The second heat exchanger 16 uses the flue gas 22 supplied to the outside of the heat transfer tube as a heat source, and circulates the combustion air 26 inside the heat transfer tube to heat the combustion air 26.
  • the flue gas 22 is heat-exchanged with the combustion air 26 in the second heat exchanger 16
  • the flue gas 22 is supplied to the cooling device 17. Also, after the combustion air 26 is heated by being heat-exchanged with the flue gas 22 in the second heat exchanger 16, the combustion air 26 is supplied to the reformer 14.
  • the cooling device 17 is intended to cool the flue gas 22.
  • the cooling device 17 is a cooling tower in which a cooling water 30 is circulated through the interior and the exterior.
  • the cooling water 30 is supplied from the tower top side, and the flue gas 22 supplied into the tower is cooled by being brought into gas-liquid contact with the cooling water 30.
  • the cooling water 30 is stored in the tower bottom, extracted to the outside, and cooled by the cooler. Thereafter, the cooling water 30 is supplied into the cooling tower again and is brought into gas-liquid contact with the flue gas 22.
  • the cooling device 17 may be a device that cools the flue gas 22 by the indirect heat-exchange with the cooling water 30, without being limited to a device that cools the flue gas 22 by bringing the flue gas 22 into direct-contact with the cooling water 30.
  • the flue gas 22 is supplied to the CO 2 recovery device 18.
  • the CO 2 recovery device 18 is intended to remove CO 2 contained in the flue gas 22.
  • the CO 2 recovery device 18 is provided on the downstream side of the second heat exchanger 16 with respect to the flow direction of the flue gas 22 of the flue gas discharging line L12.
  • a conventionally known device can be used.
  • the CO 2 recovery device 18 for example, it is possible to use a device equipped with a CO 2 absorber that absorbs CO 2 of the flue gas 22 in the CO 2 absorbent by gas-liquid contact between amine-based CO 2 absorbent and the flue gas 22 in the absorber, and a regenerator that regenerates the CO 2 absorbent by diffusing CO 2 absorbed in the CO 2 absorbent within the regenerator.
  • the raw material gas branching line L11 connects the downstream side of the desulfurization device 13 with the air supply line L15, and mixes the natural gas 21 compressed by the compressor 11 with the flue gas 22 passing through the air supply line L15, by extracting the natural gas 21 from the downstream side of the desulfurization device 13 with respect to the flow direction of the natural gas 21. Since the S content contained in the natural gas 21 is removed by the desulfurization device 13, the natural gas 21 containing no S content can be supplied to the air supply line L15. As a result, the S content is not contained in the flue gas 22 discharged from the reformer 14. As a result, since the S content in the flue gas 22 is a very small amount, an acid dew point temperature itself is lowered. Therefore, since it is possible to further reduce the flue gas temperature and increase the amount of recovery heat from the flue gas, it is possible to reduce the fuel of the reformer 14.
  • the amount of the natural gas 21, which is used as fuel in the reformer 14 for example, to about 0.7% to 8.5%.
  • Patent Literatures 1 and 2 in many cases, in general, a part of the natural gas that has not been desulfurized is extracted and used as a fuel of the reformer. Therefore, when the quantity of heat recovery of the flue gas increases and the temperature of the flue gas drops, there is a possibility that sulfuric acid corrosion occurs due to the S content such as sulfuric anhydride contained in the flue gas in a passage of a piping through which the flue gas passes.
  • the sulfuric acid corrosion refers to a phenomenon in which the temperature of the flue gas becomes the dew point temperature or lower of the acid of the S content such as sulfuric anhydride contained in the flue gas, the S content contained in the flue gas is combined with water, becomes sulfuric acid (H 2 SO 4 ) and is condensed, thereby corroding the metal. Therefore, as the material of the piping through which the flue gas passes, it is necessary to use acid-resisting steel having a high corrosion resistance against acids such as sulfuric acid.
  • the flue gas 22 discharged from the reformer 14 does not include the S content, even if the flue gas 22 is heat-exchanged with the combustion air 26 in the second heat exchanger 16 and the temperature of the flue gas 22 drops, it is possible to prevent an occurrence of corrosion in the passage of the flue gas discharging line L12 on the downstream side in the gas flow direction of the flue gas 22 from the second heat exchanger 16 of the flue gas discharging line L12. Therefore, as the material of the flue gas discharging line L12, it is possible to use other materials without being limited to the acid-resisting steel, and the application scope can be widened.
  • the heat-exchange in the second heat exchanger 16 is, for example, 175°C in view of the acid dew point, it can be lowered to the lower limit value of 120°C.
  • 120°C of the lower limit value is a flue gas temperature that is determined in consideration of the dew point of water.
  • the reducing agent 29 such as ammonia is supplied to the flue gas duct.
  • unreacted ammonia also referred to as leak ammonia
  • the ammonium sulfate may be precipitated in a heat transfer tube or a coil in the heat exchanger which heat-exchanges the flue gas and the natural gas, and may block the interior of the piping through which the flue gas passes, thereby increasing the pressure loss.
  • the ammonium hydrogen sulfate may cause corrosion in the heat exchanger which heat-exchanges the flue gas and the natural gas, and the material which forms the piping through which flue gas passes.
  • the S content does not exist in the flue gas 22 discharged from the reformer 14, even if the reducing agent 29 such as ammonia is supplied to the flue gas discharging line L12 on the upstream side of the denitrification device 15, it is possible to suppress ammonium sulfate, ammonium hydrogen sulfate or the like from being produced by the reaction of the reducing agent 29 such as unreacted ammonia with the S content.
  • the reducing agent 29 such as ammonia
  • the CO 2 recovery device 18 is provided to remove CO 2 contained in the flue gas 22, in the methods for manufacturing methanol and ammonia which have been conventionally used, as in Patent Literatures 1 and 2, it is necessary to provide the desulfurization device on the upstream side in the gas flow direction of the flue gas from the CO 2 recovery device, and the sulfur concentration in the flue gas at the inlet of the CO 2 recovery device is required to set to a predetermined value (for example, 1 ppm) or lower. Also, the number of the devices to be installed increases as much as the desulfurization device, a disposition location of each device is limited, and the installation cost increases.
  • the reforming device 10 is configured so that the first heat exchanger 12 and the second heat exchanger 16 are provided in the flue gas discharging line L12, but is not limited thereto, and the reforming device 10 may be provided with a plurality of heat exchangers for performing the heat-exchange by the flue gas 22.
  • FIG. 2 is a diagram illustrating an example of another configuration of the reforming device 10. As illustrated in FIG. 2 , the flue gas discharging line L12 has a third heat exchanger (heat exchange unit) 19 that is interposed between the first heat exchanger 12 and the second heat exchanger 16.
  • heat exchange unit heat exchange unit
  • the third heat exchanger 19 is a heat exchanger that saves heat of feed water 75 to be supplied to a steam generation unit 70. By providing the third heat exchanger 19 between the first heat exchanger 12 and the second heat exchanger 16, it is possible to increase the amount of water and the amount of heat of the feed water 75 to be supplied to the steam generation unit 70.
  • a fourth heat exchanger (heat exchange unit) 20 is provided between the compressor 11 of the raw material gas supply line L13-2 and the first heat exchanger 12 to save heat of the natural gas 21 to be supplied to the first heat exchanger 12, by the branched natural gas 21a after the desulfurization.
  • the fourth heat exchanger 20 which performs the heat-exchange between the natural gases 21, can reduce the amount of recovery heat of the flue gas 22 after the heat exchange to increase the amount of recovery heat in the third heat exchanger 19, as compared to the system illustrated in FIG. 2 .
  • the reforming device 10 is equipped with only one reformer 14, but is not limited thereto, and a plurality of reformers 14 may be equipped.
  • FIG. 4 is a diagram illustrating an example of another configuration of the reforming device 10. As illustrated in FIG. 4 , the reformer 14 may have a first reformer 14-1 and a second reformer 14-2.
  • the first reformer 14-1 is intended to supply the vapor 24 to the desulfurized and compressed natural gas 21 and primarily reform hydrocarbon in the natural gas 21 to either one or both of H 2 and CO or H 2 and CO 2 .
  • the first reformer 14-1 has the same configuration as that of the first reformer 14 illustrated in FIG. 1 , and has a main body 14a (not illustrated in FIG. 4 ), a catalyst reaction tube 14b (not illustrated in FIG. 4 ) and a burner 14c (not illustrated in FIG. 4 ).
  • the catalyst reaction tube 14b is heated by the flue gas 22 generated by combustion in the burner 14c, and the introduced natural gas 21 comes into contact with the reforming catalyst when passing through the reforming catalyst layer of the catalyst reaction tube 14b, and thus, as in the above-described formulas (3) and (4), hydrocarbon in the natural gas 21 is subjected to vapor-reforming to either one or both of H 2 and CO or H 2 and CO 2 .
  • the natural gas 21 is primarily reformed in the first reformer 14-1, it is supplied to the second reformer 14-2.
  • the second reformer 14-2 is intended to supply air (oxygen) to the reformed gas 23, and secondarily reform hydrocarbon in the reformed gas 23 using a partial oxidation reaction.
  • the heated combustion air 26 is introduced into the second reformer 14-2 from the outside, and hydrocarbon in the reformed gas 23 is secondarily reformed to either one or both of H 2 and CO or H 2 and CO 2 .
  • FIG. 5 is a diagram illustrating an example of another configuration of the reforming device 10. As illustrated in FIG. 5 , the reformer 14 may have a pre-reformer 14-3, the first reformer 14-1, and the second reformer 14-2.
  • the pre-reformer 14-3 is intended to supply the vapor 24 to the natural gas 21 and primarily reform hydrocarbon in the natural gas 21 to either one or both of H 2 and CO or H 2 and CO 2 .
  • the pre-reformer 14-3 has a main body, and a reforming catalyst layer having a reforming catalyst therein. Also, the pre-reformer 14-3 is connected to the vapor supply line L14. The vapor 24 is supplied into the pre-reformer 14-3 through the vapor supply line L14, and is mixed with the natural gas 21. After the natural gas 21 is mixed with the vapor 24 in the main body, the natural gas 21 is supplied to the reforming catalyst layer.
  • the natural gas 21 comes into contact with the reforming catalyst when passing through the reforming catalyst layer in the pre-reformer 14-3, and thus, as in the above-described formulas (3) and (4), hydrocarbon in the natural gas 21 is primarily reformed to either one or both of H 2 and CO or H 2 and CO 2 .
  • the reformer 14 When the reformer 14 is constituted by three stages of the first reformer 14-1, the second reformer 14-2 and the pre-reformer 14-3, a part or all of the flue gas 22 discharged from the first reformer 14-1 may be used as a heating medium for heating the reforming catalyst layer of the pre-reformer 14-3.
  • FIGS. 6 to 8 are diagrams illustrating modified examples of another configuration of the reforming device 10.
  • the raw material gas branching line L11 is provided so as to be connected to the air supply line L15 so that the natural gas 21 and the combustion air 26 are supplied to the reformer 14 through the air supply line L15, but is not limited thereto, and as illustrated in FIG. 6 , the raw material gas branching line L11 may be directly connected to the reformer 14 so that the natural gas 21 and the combustion air 26 are separately supplied into the reformer 14.
  • the raw material gas branching line L11 is provided so as to be connected to the downstream side of the desulfurization device 13 with respect to the flow direction of the natural gas 21, but is not limited thereto, and as illustrated in FIG. 7 , a raw material gas branching line L21 for connecting the upstream side of the desulfurization device 13 with the air supply line L15 may be provided such that the raw material gas branching line L21 extracts the branch gas 21b of a part of the natural gas 21 from the upstream side of the desulfurization device 13 with respect to the flow direction of the natural gas 21.
  • the raw material gas branching lines L11 and L21 may be provided so as to extract 21a of a part of the natural gas 21 from the upstream side and the downstream side of the desulfurization device 13 with respect to the flow direction of the natural gas 21.
  • the reforming device 10 is equipped with the denitrification device 15, but is not limited thereto, and the reforming device 10 may not be equipped with the denitrification device 15.
  • the reforming device 10 is equipped with the cooling device 17 and the CO 2 recovery device 18, but is not limited thereto, and the reforming device 10 may not be equipped with these devices in a case where there is no need for recovery of CO 2 contained in the flue gas 22.
  • the reforming device 10 since the reforming device 10 has the characteristics as described above, it can be used for manufacturing the chemical products, using the reformed gas 23 obtained in the reforming device 10.
  • the chemical products include, for example, ammonia, methanol, urea, hydrogen, and liquid fuel of liquid hydrocarbon such as wax, diesel oil, kerosene, and gasoline by FT synthesis.
  • the reforming device 10 by applying the reforming device 10 to the manufacturing system of ammonia and methanol and the manufacturing system of urea and methanol, it is possible to improve the manufacturing efficiency of methanol and ammonia, and the manufacturing efficiency of urea and methanol.
  • FIGS. 9 and 10 are diagrams illustrating examples of system configurations of the reforming device illustrated in FIG. 1 and the reforming device illustrated in FIG. 3 .
  • FIG. 9 is an example of a system configuration corresponding to the reforming device illustrated in FIG. 1 , and the flue gas 22 introduced into the flue gas discharging line L12 from the reformer 14 is heat-exchanged in a plurality of heat exchange units provided inside the flue gas duct.
  • the heated natural gas 21 passes through the desulfurization device 13, is further heat-exchanged in a heat exchanger (not illustrated), and is introduced into the reformer 14 side.
  • T 4 120°C
  • the temperature of the reformer 14 becomes a high temperature side, it is possible to reduce an amount of branch of the natural gas 21 to be introduced into the reformer 14 in the flue gas discharging line L12, thereby improving the amount of introduction of the natural gas 21 for reforming.
  • FIG. 10 is an example of the system configuration corresponding to the reforming device illustrated in FIG. 3 .
  • the heated natural gas 21 is then heated to about 360°C by a heat exchanger which is not illustrated, passes through the desulfurization device 13, is further heat-exchanged in a heat exchanger which is not illustrated, and is introduced into the reformer 14 side.
  • the flue gas 22 is heat-recovered by a heat exchanger (not illustrated), and becomes to have the temperature of about 350°C on the downstream side of the denitrification device 15.
  • the heated feed water 75 is introduced into the steam generation unit 70.
  • the amount of water of the feed water 75 of the vapor generation to be introduced into the steam generation unit 70 increases by the reforming system of FIG. 10 , the amount of steam generation is improved by about 20 t/h compared to the case of the reforming system of FIG. 9 , and it is possible to achieve a reduction of 1.9% in the product basic unit of ammonia (Gcal/ton-NH 3 ) including the installation of an auxiliary boiler.
  • the manufacturing device of chemical products has the reforming device 10, and a chemical product generation unit that manufactures the chemical products using the reformed gas 23 obtained by the reforming device 10.
  • a chemical product generation unit that manufactures the chemical products using the reformed gas 23 obtained by the reforming device 10.
  • ammonia, methanol or urea as the chemical products
  • FIG. 11 is a schematic diagram of a chemical product manufacturing device equipped with the reforming device according to a second embodiment of the present invention.
  • the reforming device having the two-stage configuration illustrated in FIG. 4 is used. Since the same configurations as those of the reforming device according to the first embodiment illustrated in FIG. 4 are identical, the repeated description will not be provided.
  • the reformer is configured so that the primary reformer 14 has a primary reformer 14-1 and a secondary reformer 14-2, but the present invention is not limited thereto.
  • a chemical product manufacturing device 40 for manufacturing ammonia has a reforming device 10, a steam generation unit 70, a CO shift reaction device (CO shift reaction unit) 41, a carbon dioxide removal device (carbon dioxide removal unit) 42, a methanation device (methanation unit) 43, a compressor 44, a hydrogen separation device (hydrogen separation unit) 45, an ammonia synthesis unit 46, a cooling unit 72, and a separation unit 73.
  • the CO shift reaction device 41, the carbon dioxide removal device 42, the methanation device 43, compressors 44-1 and 44-2, the hydrogen separation device 45 and the ammonia synthesis unit 46 form a chemical product generation unit.
  • first and second preliminary heating units 76-1 and 76-2 which preliminarily heat the feed water 75 to be supplied to the steam generation unit 70, are interposed between the CO shift reaction device (CO shift reaction unit) 41 and the carbon dioxide removal device (carbon dioxide removal unit) 42, and between the ammonia synthesis unit 46 and the cooling unit 72.
  • a steam header 80 supplies the vapor obtained by the steam generation unit 70.
  • the vapor from an auxiliary boiler or the like is also introduced into the steam header, and a required amount of vapor is sent to each vapor supply destination from here.
  • the steam generation unit 70 is intended to supply the vapor 24 to the steam header 80 in the system.
  • the steam generation unit 70 is provided with a waste heat recovery boiler (WHB) which recovers the waste heat of the reformed gas 23, and a superheater. After the steam generation unit 70 thermally heats the feed water 75 by the waste heat to obtain the heated vapor, the steam generation unit 70 further overheats the heated vapor by the superheater and sends the vapor 24 to the steam header 80.
  • the waste heat recovery boiler may be further installed on the downstream side of the passage line of the reformed gas 23 and on the downstream side of the ammonia synthesis unit 46 to recover the heat, but the waste heat recovery boiler is not provided in this embodiment.
  • the CO shift reaction device 41 is intended to convert (shift) CO in the reformed gas 23 to CO 2 and generate a shift gas 51 containing CO 2 .
  • a CO shift reactor equipped with a filling unit filled with the CO shift reaction catalyst which converts (shift) CO to CO 2 is used.
  • the reformed gas 23 obtained by reforming the natural gas 21 in the reforming device 10 is discharged from the reforming device 10 and is supplied to the CO shift reaction device 41.
  • CO in the reformed gas 23 is converted to CO 2 to generate a shift gas 51 containing CO 2 .
  • the gas temperature of the shift gas 51 is, for example, in the range of 150°C to 1000°C.
  • the shift gas 51 generated by the CO shift reaction device 41 is discharged from the CO shift reaction device 41 and is supplied to the carbon dioxide removal device 42.
  • the carbon dioxide removal device 42 is intended to remove carbon dioxide (CO 2 ) in the shift gas 51.
  • CO 2 carbon dioxide
  • a device which removes CO 2 in the shift gas 51 by utilizing a chemical adsorption using CO 2 absorbent such as an amine solvent, a device having catalyst for removing CO 2 , a membrane separation device having a separation membrane which separates CO 2 in the shift gas 51 or the like is used.
  • the carbon dioxide removal device 42 removes CO 2 in the shift gas 51 to generate a CO 2 removal gas 52 from which CO 2 is removed.
  • the gas temperature of the CO 2 removal gas 52 is, for example, about 50°C.
  • the carbon dioxide removal device 42 separates CO 2 from the shift gas 51.
  • separated CO 2 may be used as a gas for methanol synthesis.
  • the CO 2 removal gas 52 discharged from the carbon dioxide removal device 42 is supplied to the methanation device 43.
  • the methanation device 43 is intended to convert CO 2 in the CO 2 removal gas 52, from which CO 2 is removed by the carbon dioxide removal device 42, into methane.
  • a methanation reactor (methanator) having a catalyst portion filled with methanation catalyst inside or the like is used as the methanation device 43.
  • the reaction temperature (methanation temperature) at the catalyst portion is preferably 220°C or higher and 450°C or lower, and more preferably, 290°C or higher and 350°C or lower, from the viewpoint of the limit temperature at which the methanation catalyst can be used.
  • CO 2 in the CO 2 removal gas 52 is converted into methane to generate a CO 2 removal gas 53 containing methane.
  • the CO 2 removal gas 53 discharged from the methanation device 43 is supplied to the compressor 44.
  • the compressor 44 is intended to compress the CO 2 removal gas 53.
  • the CO 2 removal gas 53 After raising the pressure of the CO 2 removal gas 53 by the compressor 44, the CO 2 removal gas 53 is supplied to the hydrogen separation device 45.
  • the ammonia synthesis unit 46 is intended to manufacture ammonia (NH 3 ) 55 after converting CO 2 in the CO 2 removal gas 53 into methane by the methanation device 43. It is possible to use an ammonia synthesis unit 46 that has been generally used hitherto, and, for example, it is possible to adopt an ammonia synthesis reactor in which the catalyst is disposed on one or more beds in the reactor. A method for synthesizing ammonia by causing the CO 2 removal gas 53 as a synthesis gas containing nitrogen (N 2 ) and hydrogen to flow through the ammonia synthesis reactor is used.
  • the ammonia composite obtained in the ammonia synthesis unit 46 passes through the second preheating unit 76-2, the ammonia composite is cooled by the cooling unit 72, and the objective ammonia 55 is separated by the separation unit 73.
  • the chemical product manufacturing device 40 for manufacturing ammonia it is possible to improve the thermal efficiency when reforming the natural gas 21 by providing the above-described reforming device 10, and it is possible to suppress an occurrence of corrosion in the passage of the flue gas discharging line L12 in the course of processing the flue gas 22. Therefore, according to the chemical product manufacturing device 40 that manufactures ammonia, it is possible to stably produce the ammonia 55 and to improve the production efficiency of the ammonia 55.
  • the sulfur content is removed in the desulfurization device 13, it is possible to lower the temperature of the flue gas 22 after the heat exchange to 120°C, and it is possible to increase the heat exchange efficiency in the second heat exchanger 16 of the flue gas discharging line L12. That is, since the sulfur content is not removed in the related art, the temperature of the flue gas 22 can only be lowered to about 175°C, the amount of introduction of the branch fuel increases accordingly, and as a result, the amount of production of the reformed gas decreases.
  • the chemical product manufacturing device of the present embodiment since it is possible to raise the temperature of the combustion air 26 to be introduced into the reformer 14, it is possible to reduce an amount of branch of the natural gas 21 that is introduced to the reformer 14 by being branched. As a result, since it is possible to achieve an increase in the amount of production of the reformed gas, it is possible to increase the amount of manufacturing of ammonia.
  • FIG. 12 is a schematic diagram of the chemical product manufacturing device equipped with the reforming device illustrated in FIG. 3 according to the second embodiment of the present invention.
  • the reforming device illustrated in FIG. 3 is configured so that the reformer 14 is one stage, but in this example, a reformer of a two-stage configuration is adopted as illustrated in FIG. 4 .
  • a third heat exchanger 19 is interposed between the first heat exchanger 12 and the second heat exchanger 16 provided in the flue gas discharging line L12.
  • a steam superheater 89 which heat-exchanges the vapor 24 from the steam generation unit 70, is provided in the flue gas discharging line L12.
  • the auxiliary boiler may not be required or the auxiliary boiler can be significantly reduced in size.
  • the chemical product manufacturing device 40 for manufacturing ammonia it is possible to improve the thermal efficiency when reforming the natural gas 21 by providing the reforming device 10, and it is possible to suppress an occurrence of corrosion in the passage of the flue gas discharging line L12 in the course of processing the flue gas 22. Therefore, according to the chemical product manufacturing device 40 of the present embodiment, it is possible to stably produce the ammonia 55 and to improve the production efficiency of the ammonia 55.
  • FIG. 13 is a schematic diagram of the chemical product manufacturing device equipped with the reforming device according to the second embodiment of the present invention.
  • FIG. 13 is a schematic diagram of a manufacturing system of urea and methanol according to the second embodiment of the present invention.
  • a chemical product manufacturing device 40 for manufacturing urea is further equipped with a urea synthesis unit 61 and a carbon dioxide branching supply line L33, in the chemical product manufacturing device 40 illustrated in FIG. 12 .
  • the urea synthesis unit 61 is provided on the downstream side in the ammonia flow direction of the ammonia synthesis unit 46.
  • the urea synthesis unit 61 is intended to synthesize a urea 62 using the ammonia 55 obtained in the ammonia synthesis unit 46. It is possible to use the urea synthesis unit 61 which has been generally used hitherto, and for example, it is possible to adopt a urea synthesis tube in which ammonia and CO 2 react with each other in the tube.
  • the carbon dioxide branching supply line L33 is a line that introduces CO 2 , which has been removed by the carbon dioxide removal device 42, into the urea synthesis unit 61.
  • the ammonia 55 obtained in the ammonia synthesis unit 46 is supplied to the urea synthesis unit 61.
  • the ammonia 55 is supplied from the carbon dioxide removal device 42 to the urea synthesis unit 61 from the carbon dioxide supply line L33.
  • the ammonia 55 obtained in the ammonia synthesis unit 46 and CO 2 separated by the carbon dioxide removal device 42 react with each other as in the following reaction formula (9) to synthesize urea (NH 2 (CO)NH 2 ).
  • the chemical product manufacturing device 40 that manufactures urea
  • FIG. 14 is a schematic diagram of the chemical product manufacturing device equipped with the reforming device according to a second embodiment of the present invention.
  • ammonia or urea has been manufactured alone.
  • the chemical product manufacturing device a device capable of simultaneously manufacturing methanol as well as ammonia is provided.
  • the chemical product manufacturing device 40 for manufacturing of ammonia and methanol has a reforming device 10, a CO shift reaction device (CO shift reaction unit) 41, a carbon dioxide removal device (carbon dioxide removal unit) 42, a methanation device (methanation unit) 43, first and second compressors 44-1 and 44-2, an ammonia synthesis unit (ammonia synthesis unit) 46, and a methanol synthesis unit 47.
  • the methanol synthesis unit 47 is installed on the upstream side of the methanation device 43.
  • the first compressor 44-1 is installed between the carbon dioxide removal device 42 and the methanol synthesis unit 47
  • the second compressor 44-2 is installed between the methanation device 43 and the ammonia synthesis unit 46.
  • the compressor 44 has a two-stage configuration, it may have a plurality of stages such as a three-stage configuration of a low-pressure compressor, an intermediate-pressure compressor and a high-pressure compressor.
  • the methanol synthesis unit 47 is intended to synthesize the methanol 56 that uses carbon dioxide and hydrogen in the reformed gas 23 obtained in the reforming device 10 as a raw material. It is possible to use the methanol synthesis unit 47 that has been generally used hitherto, and for example, a methanol synthesis device having a catalytic reactor or the like is used.
  • carbon dioxide in the reformed gas 23 as a methanol production raw material adjusts its content, by providing bypass lines L35 and L36 each having on-off valves V 1 and V 2 that partially bypass the CO shift reaction device 41 and the carbon dioxide removal device 42.
  • the chemical product manufacturing device 40 that manufactures ammonia and methanol, it is possible to obtain the ammonia 55 obtained in the ammonia synthesis unit 46 and the methanol 56 obtained in the methanol synthesis unit 47, and it is possible to simultaneously manufacture the ammonia 55 and the methanol 56 in parallel.
  • the chemical product manufacturing device 40 that manufactures ammonia and methanol by providing the reforming device 10 of the first embodiment, similar to the chemical product manufacturing device 40 that manufactures ammonia according to the second embodiment, it is possible to improve the thermal efficiency when reforming the natural gas 21 and it is possible to prevent the occurrence of corrosion in the passage of the flue gas discharging line L12 in the course of processing the flue gas 22. Therefore, according to the chemical product manufacturing device 40 that manufactures urea, it is possible to stably produce the ammonia 55 and the methanol 56 and to improve their production efficiency.
  • FIG. 15 is a schematic diagram of a chemical product manufacturing device equipped with the reforming device according to the second embodiment of the present invention.
  • ammonia and methanol have been manufactured in the above-described embodiments, in this embodiment, as a chemical product manufacturing device, there is provided a device capable of manufacturing urea and simultaneously manufacturing methanol, by using ammonia as a raw material.
  • the ammonia 55 obtained in the ammonia synthesis unit 46 is further introduced into the urea synthesis unit 61 to manufacture urea.
  • the chemical product manufacturing device 40 that manufactures urea and methanol, it is possible to obtain the urea 62 using the ammonia 55 obtained in the ammonia synthesis unit 46 as a raw material, and the methanol 56 obtained in the methanol synthesis unit 47, and it is possible to simultaneously obtain the urea 62 and the methanol 56 in parallel.
  • the chemical product manufacturing device 40 that manufactures urea and methanol by providing the reforming device 10 of the first embodiment, similar to the chemical product manufacturing device 40 that manufactures ammonia according to the second embodiment, it is possible to improve the thermal efficiency when reforming the natural gas 21 and it is possible to suppress the occurrence of corrosion in the passage of the flue gas discharging line L12 in the course of processing the flue gas 22. Therefore, according to the chemical product manufacturing device 40 that manufactures urea, it is possible to stably produce the urea 62 and the methanol 56 and to improve their production efficiency.
  • FIG. 16 is a schematic diagram of a chemical product manufacturing device equipped with the reforming device according to the second embodiment of the present invention.
  • methanol has been manufactured by the reformed gas 23
  • the chemical product manufacturing device a device capable of manufacturing methanol by the additional methanol synthesis unit by separating carbon dioxide and hydrogen from the reformed gas 23 is provided.
  • a hydrogen separation device 45 is provided between the first compressor 44-1 and the second compressor 44-2.
  • the hydrogen separation device 45 provided between the first compressor 44-1 and the second compressor 44-2 is intended to separate a part of hydrogen (H 2 ) contained in the CO 2 removal gas 53 from the CO 2 removal gas 53.
  • the hydrogen separation device 45 is a membrane separation device having a hydrogen-permeable function membrane.
  • the hydrogen-permeable function membrane is a membrane for separating at least a part of hydrogen (H 2 ) contained in the gas.
  • the hydrogen-permeable function membrane for example, it is preferred to use a palladium (Pd) membrane, a polymer membrane such as polysulfone, polyamide or polyimide, or a membrane obtained by a plurality of bundles of elements formed into a hollow fiber.
  • a palladium (Pd) membrane a polymer membrane such as polysulfone, polyamide or polyimide, or a membrane obtained by a plurality of bundles of elements formed into a hollow fiber.
  • the hydrogen-permeable function membrane it is possible to adopt the most suitable design, based on the material, the use condition, the life, the hydrogen permeation coefficient, and the selection rate.
  • the hydrogen separation device 45 since the CO 2 removal gas 53 transmits through the hydrogen-permeable function membrane, hydrogen contained in the CO 2 removal gas 53 is separated by the hydrogen permeable function membrane.
  • the CO 2 removal gas 53 in which hydrogen is separated by the hydrogen separation device 45 is discharged from the hydrogen separation device 45.
  • the hydrogen separation device 45 is connected to the hydrogen supply line L32, a part of hydrogen (H 2 ) separated from the shift gas 51 in the hydrogen separation device 45 is supplied to the methanol synthesis unit 47 through the hydrogen supply line L32, and is used as a gas for methanol synthesis.
  • a membrane separation device equipped with the hydrogen-permeable function membrane is used, but is not limited thereto, and, for example, it is possible to use a pressure swing adsorption device (PSA) or the like, and any device capable of separating at least a part of hydrogen contained in the CO 2 removal gas 53 may be used.
  • PSA pressure swing adsorption device
  • the CO 2 removal gas 53 discharged from the hydrogen separation device 45 is supplied to the second compressor 44-2. After the pressure of the CO 2 removal gas 53 is appropriately adjusted to a pressure suitable for ammonia synthesis in the second compressor 44-2, the CO 2 removal gas 53 is supplied to the ammonia synthesis unit 46. Furthermore, hydrogen separated by the hydrogen separation device 45 is supplied to the methanol synthesis unit 47 through a hydrogen supply line L32.
  • Hydrogen separated by the hydrogen separation device 45 passes through the hydrogen supply line L32, CO 2 separated by the carbon dioxide removal device 42 passages through the carbon dioxide supply line L31, and hydrogen separated by the hydrogen separation device 45 and carbon dioxide (CO 2 ) separated by the carbon dioxide removal device 42 are supplied to the methanol synthesis unit 47.
  • the methanol synthesis unit 47 is intended to synthesize the methanol 56, by using carbon dioxide separated by the carbon dioxide removal device 42 and hydrogen separated by the hydrogen separation device 45, as the raw materials. It is possible to use the methanol synthesis unit 47 that has been generally used hitherto, and for example, a methanol synthesis device having a catalytic reactor or the like is used.
  • the chemical product manufacturing device 40 that manufactures the ammonia 55 and the methanol 56, it is possible to obtain the ammonia 55 obtained in the ammonia synthesis unit 46, and the methanol 56, by using carbon dioxide separated by the carbon dioxide removal device 42 and hydrogen separated by the hydrogen separation device 45, and it is possible to simultaneously manufacture the ammonia 55 and the methanol 56 in parallel.
  • the manufacturing system 40 that manufactures ammonia and methanol, by providing the reforming device 10, it is possible to improve the thermal efficiency when reforming the natural gas 21, and it is possible to suppress the occurrence of corrosion in the passage of the flue gas discharging line L12 in the course of processing the flue gas 22. Therefore, according to the manufacturing system 40 of ammonia and methanol, it is possible to stably produce the ammonia 55 and the methanol 56 and to improve the production efficiency of the ammonia 55 and the methanol 56.
  • the hydrogen separation device 45 is provided between the first compressor 44-1 and the second compressor 44-2 to separate hydrogen in all CO 2 removal gas 53 separated by the hydrogen separation device 45.
  • the above-described configuration is not limited, and only a part of the CO 2 removal gas 53 separated by the first compressor 44-1 or the second compressor 44-2 may be supplied to the hydrogen separation device 45 to separate hydrogen in the CO 2 removal gas 53 by the hydrogen separation device 45.
  • FIG. 17 is a schematic diagram of a chemical product manufacturing device equipped with the reforming device according to the second embodiment of the present invention.
  • the ammonia 55 and the methanol 56 are manufactured in the embodiment of FIG. 16
  • a device capable of manufacturing urea by the urea synthesis unit 61 from the obtained ammonia 55 is provided.
  • the ammonia 55 obtained in the ammonia synthesis unit 46 is further introduced into the urea synthesis unit 61 to manufacture urea in the chemical product manufacturing device 40 of FIG. 14 .
  • the chemical product manufacturing device 40 that manufactures urea and methanol according to the present embodiment, it is possible to obtain the urea 62 using the ammonia 55 obtained in the ammonia synthesis unit 46 as the raw material, and the methanol 56 obtained in the methanol synthesis unit 47, and it is possible to simultaneously manufacture the urea 62 and the methanol 56 in parallel.
  • the chemical product manufacturing device 40 that manufactures urea and methanol by providing the reforming device 10 of the first embodiment, similar to the chemical product manufacturing device 40 that manufactures ammonia according to the second embodiment, it is possible to improve the thermal efficiency when reforming the natural gas 21, and it is possible to suppress the occurrence of corrosion in the passage of the flue gas discharging line L12 in the course of processing the flue gas 22. Therefore, according to the chemical product manufacturing device 40 that manufactures urea, it is possible to stably produce the urea 62 and the methanol 56 and to improve their production efficiency.
  • FIGS. 18 and 19 are schematic diagrams of the chemical product manufacturing device equipped with the reforming device according to the second embodiment of the present invention.
  • a device for manufacturing only methanol is provided as the chemical product manufacturing device.
  • the chemical product manufacturing device 40 for manufacturing methanol has a reforming device 10, a steam generation unit 70, a compressor 44, and a methanol synthesis unit 47.
  • the chemical product manufacturing device 40 of the present embodiment is intended to synthesize the methanol 56, by using carbon dioxide and hydrogen in the reformed gas 23 obtained in the reforming device 10 as the raw material. It is possible to use the methanol synthesis unit 47 that has been generally used hitherto, and for example, a methanol synthesis device having a catalytic reactor is used.
  • the reformer 14 has a two-stage configuration
  • the first reformer 14-1 has the configuration of the reformer of FIG. 1
  • the second reformer 14-2 is used as an auto-thermal reforming furnace (ATR: Auto Thermal Reformer), and oxygen in place of air is supplied to the reformer to obtain a reformed gas 23 having a gas composition that is suitable for methanol synthesis.
  • ATR Auto Thermal Reformer
  • the second embodiment although the description has been given of a case where ammonia, methanol or urea is manufactured by alone or in co-production, the second embodiment is not limited thereto, and it can also be similarly applied to a case where ammonia or urea and other hydrocarbon are simultaneously manufactured in parallel.
  • the reforming device 10 can also be similarly used in a hydrogen manufacturing system that manufactures hydrogen, and a system that manufactures liquid fuel of liquid hydrocarbon by the FT synthesis. Also, it may be manufactured by combining a plurality of these chemical products.

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EP13837204.0A 2012-09-12 2013-09-03 Reformierungsvorrichtung und reformierungsverfahren, vorrichtung zur herstellung chemischer produkte mit einer reformierungsvorrichtung und verfahren zur herstellung chemischer produkte Withdrawn EP2896596A4 (de)

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PCT/JP2012/073374 WO2014041645A1 (ja) 2012-09-12 2012-09-12 改質装置およびそれを備えた化成品の製造装置
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US10759744B2 (en) 2017-04-05 2020-09-01 Johnson Matthey Public Limited Company Process for the production of formaldehyde-stabilized urea
CN112403154A (zh) * 2019-11-05 2021-02-26 中冶长天国际工程有限责任公司 一种烟气多污染物协同净化工艺及装置
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EP3974378A1 (de) * 2020-09-25 2022-03-30 Yara International ASA Verfahren zur erwärmung einer einspeisung von erdgas in einen dampfreformer und system und verwendung davon
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US10258960B2 (en) 2019-04-16
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CN104583121A (zh) 2015-04-29
US20150202589A1 (en) 2015-07-23
US9737868B2 (en) 2017-08-22
WO2014041645A1 (ja) 2014-03-20
EP2896596A4 (de) 2016-06-29
US20170096333A1 (en) 2017-04-06
WO2014042042A1 (ja) 2014-03-20
CN104583121B (zh) 2016-10-12
RU2606606C2 (ru) 2017-01-10

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